US3407168A - Alkylbenzenes as diluents for elastomeric olefin polymers - Google Patents
Alkylbenzenes as diluents for elastomeric olefin polymers Download PDFInfo
- Publication number
- US3407168A US3407168A US538871A US53887166A US3407168A US 3407168 A US3407168 A US 3407168A US 538871 A US538871 A US 538871A US 53887166 A US53887166 A US 53887166A US 3407168 A US3407168 A US 3407168A
- Authority
- US
- United States
- Prior art keywords
- ethylene
- preadix
- vulcanizates
- mixes
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003085 diluting agent Substances 0.000 title description 23
- 150000004996 alkyl benzenes Chemical class 0.000 title description 13
- 229920000098 polyolefin Polymers 0.000 title 1
- 239000000203 mixture Substances 0.000 description 56
- 239000003921 oil Substances 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 23
- 238000004073 vulcanization Methods 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 150000002978 peroxides Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000012763 reinforcing filler Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000010690 paraffinic oil Substances 0.000 description 5
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- -1 decyl- Chemical group 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 239000004614 Process Aid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- MCVUKOYZUCWLQQ-UHFFFAOYSA-N tridecylbenzene Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1 MCVUKOYZUCWLQQ-UHFFFAOYSA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004997 alkyl benzene derivatives Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012345 traction test Methods 0.000 description 1
- SYOKIDBDQMKNDQ-XWTIBIIYSA-N vildagliptin Chemical compound C1C(O)(C2)CC(C3)CC1CC32NCC(=O)N1CCC[C@H]1C#N SYOKIDBDQMKNDQ-XWTIBIIYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
Definitions
- ABSTRACT OF THE DISCLOSURE Amorphous vulcanizable copolymers of ethylene and propylene or butene-l are extended by mixing the same with monoalkylbenzenes, polyalkylbenzenes, or mixtures thereof.
- the extenders comprise an aromatic nucleus having one or more linear or branched alkyl substituents containing from 1 to 20, preferably from 10 to 20, carbon atoms.
- the present invention relates to vulcanizable compositions based on amorphous polymers of ethylene with an alpha-olefin containing as a plasticizer, extending or diluting agent, a monoor poly-alkylbenzene, and to the vulcanized articles obtained therefrom. More particularly, it relates to the dilution with monoor poly-alkylbenzenes of linear, amorphous, saturated copolymer of ethylene with propylene or butene-l, and to the vulcanized products thus obtained.
- the vulcanization product is not influenced, or only influenced to a minor extent, by the addition of either small, or even relatively large, amount of mineral oils.
- An object of the present invention is a vulcanizable composition based on saturated amorphous copolymers of ethylene with a higher alpha-olefin, such as propylene or butene-l, extended or plasticized with products which inter-react very little with the vulcanizing agents, remarkably less than the best parafiinic oils.
- the ethylene-alpha-olefin copolymers preferably used according to the present invention are the ethylene-propylene or ethylene-butene-l copolymers having a molar ethylene content from 20 to 80% and a molecular weight between 50,000 and 800,000, preferably between 60,000 and 500,000.
- the dilution according to the present invention consists of adding to a copolymer as defined above, and having a viscosity ML (1+4) 100 C. (ASTM D-1646-61) not lower than 20, and a molar ethylene content between -nited States Patent 20 and an alkyl benzene derivative in amount from 5 to 200 parts by weight per parts of polymer, in the presence of vulcanization agents, reinforcing fillers, and of other ingredients commonly used in the vulcanization industry.
- the present invention thus relates to a vulcanizable composition based on amorphous copolymers'of ethylene with an alpha-olefin, containing a reinforcing filler, vulcanizing agents, an extending agent, possibly an antioxidant, characterized in that the extending agentis, selected from the group consisting of monoalkylbenzenes, polyalkylbenzenes and mixtures'thereof, consisting 'of an aromatic nucleus having one or more linear or branched alkyl substituents containing from 1 to 20 carbonatoms.
- the alkylbenzenes can be easily obtained by Friedel- Crafts synthesis or by other common synthesis reactions.
- the alkylbenzene dilution agents preferably have a viscosity varying from 2 to 100 centistokes at 100 C., a molecular weight comprised between 220 and 700 and should not contain moisture and various impurities; they must also have a good flow at low temperatures, a high flash point and boiling point, a low content of ashes and of total acidity.
- exemplary products are pure dodecylbenzene and the commercial product is Preadix 8.
- Preadix 8 is a mixture consisting of 50% of monoalkylbenzenes and 50% of polyalkylbenzenes in which the alkyl groups have a branched chain and contain about 15 carbon atoms.
- Asphalt and resins Absent Absent. Active sulfur Absent. Corrosion test on copper Negative. Ash Traces. Boiling point Above 300 C. Index of refraction (11 1.4899. Aniline point 69.5 C.
- alkylbenzene that gives particularly good results is a mixture of decyl-, undecyl-, dodecyland tridecyl-benzene.
- the technique of addition of these diluents can be that usually adopted for the plasticizers, by operating in an open or inner mixer.
- the diluents can be added during the polymerization or in the successive stages.
- the fillers, other ingredients and the vulcanization agents are then added to these mixtures of diluent and copolymer.
- the reinforcing agent used can be of any type, more particularly of basic type, carbon black of any type, or a white mineral filler.
- the amount of reinforcingfiller to be used is between 10 and 200%, preferably'between 30 and by weight, referred to the copolymer.
- the vulcanization agents to be used are organic peroxides, in amount from 0.1 to 10 parts by weight per 100 parts of copolymer. Any organic peroxide can be used; the most commonly used are dibenzoylperoxide,
- dicumyl peroxide, tert.buty1peroxide, tert.butyl perbenzodiluent, carbon black and sulfur are prepared, while the ate and a,a'-bis(tert.butylperoxy)diisopropylbenzene, peroxide is added in an open mixer.
- a free-radical acceptor in amount lower than the half The compositions of the mixes and the main mechanical by weight of the amount of peroxide may also be used. characteristics are reported in Table 1. As free-radical acceptor, sulfur, quinonic compounds, In the mixes containing the parafiinic oil, the forming furfural and its derivatives can be used. of the mix being the same, the interference of the oil with The vulcanization is carried out by heating the mixes the vulcanizing action of the peroxide is evident. Preadix to temperatures between 110 and 220 C., preferably be- 8, on the other hand, interferes to a minimum extent, and tween 140 and 180. C.
- the vulcanizates containing paratfinic oil are poor, and even with 9 parts of crosslinking agent, they do not reach the characteristics of the vulcanizates containing diluent Preadix 8 and only 5 parts of peroxide. Also, with the same cross-linking agent amount, the better elasticity (lower permanent set) of the vulcanizates containing Preadix 8 is further pointed out.
- Ethylene-propylene copolymer (50% by mole of ethylene and ML (14) 100 C. 10) 75 75 75 75 75 75 75 75 75 75 Oil FL-65 (p aratfinic) l l 25 25 25 25 25 Oil Preadix 25 25 25 25 25 Carbon black HAF... 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50
- the Garvey die makes it possible I to extrude through a trapezoidal section, an extruded article which is evaluated on the basis of its section, top, surface and corners. To each parameter a score, from 1 to 4, 4 being very good, is given. The extrudability index is the sum of the four values given to each parameter. The maximum value is 16.
- mix AB decylundecyl-dodecyl-tridecylbenzenes
- composition according to claim 1 in which the alkyl substituent is linear.
- composition according to claim 1 in which the alkyl substituent is branched.
- alkylbenzene extending agent is a mixture of alkylbenzones, in which the alkyl substituent of the various members of the mixture varies from 10 to 20 carbon atoms.
- composition according to claim 1 in which the alykylbenzene compound is pure dodecyl benzene.
- composition according to claim 1 in which the extending agent is a mixture of about of monoalkylbenzenes and about 50% of polyalkylbenzenes in which the alkyl groups have a branched chain and contain about 15 carbon atoms.
- composition according to claim 1 in which the extending agent is used in amount from 5 to 200 parts by weight per 100 parts of polymer.
- composition according to claim 1 in which the higher alpha-olefin is propylene.
- composition according to claim 1 in which the higher alpha-olefin is butene-l.
- composition according to claim 1 in which the ethylene content is from 20 to 12.
- composition according to claim 9 in which the viscosity of the polymer, as determined according to ASTM D-1646-61, is at least 20.
- composition according to claim 15 which also contains an antioxidant.
- composition according to claim 15 in which an organic peroxide in amount from 0.1 to 10 parts by Weight per parts of copolymer is used as vulcan'izing agent.
- composition according to claim 18, in which the free-radical acceptor is selected from the group consisting of sulfur, quinonic compounds, furfural and its derivatives.
- a process for preparing vulcanizates having high mechanical properties comprising preparing a vulcanizable composition containing a saturated amorphous copolymer of ethylene and a higher alpha-olefin selected from the group consisting of propylene and butene-l, a reinforcing filler, a vulcanizing agent and an extending agent for the copolymer selected from the group consisting of monoalkylbenzenes, polyalkylbenzenes and mixtures thereof, said benzenes having an aromatic nucleus and at least one alkyl substituent containing 10 to 20 carbon atoms, and then vulcanizing this mixture at a temperature between and 220 C.
- composition contains 5 to 200 parts by weight of extending agent per 100 parts of polymer.
- a process according to claim 22, for preparing low hardness articles in which, in the vulcanizable composition, an amount of extending .agent of at least 1 part for every 2 parts by weight of polymer is used, and in which an amount of filler of at least 6 parts for every 10 parts by weight of polymer is used.
- Vulcanized elastomers obtained according to the process of claim 22.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT706065 | 1965-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3407168A true US3407168A (en) | 1968-10-22 |
Family
ID=11123807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US538871A Expired - Lifetime US3407168A (en) | 1965-03-31 | 1966-03-30 | Alkylbenzenes as diluents for elastomeric olefin polymers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3407168A (forum.php) |
| BE (1) | BE678686A (forum.php) |
| CH (1) | CH467294A (forum.php) |
| DE (1) | DE1694577B2 (forum.php) |
| ES (1) | ES324899A1 (forum.php) |
| GB (1) | GB1131915A (forum.php) |
| NL (1) | NL150484B (forum.php) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2885378A (en) * | 1956-05-14 | 1959-05-05 | Monsanto Chemicals | Composition containing halogenated vinylidene resin plus non-volatile liquid monophenyl alkane plasticizer |
| US3296184A (en) * | 1963-02-14 | 1967-01-03 | Montedison Spa | Vulcanizable compositions of olefin polymers or copolymers and vulcanized articles obtained therefrom |
-
1966
- 1966-03-29 GB GB13786/66A patent/GB1131915A/en not_active Expired
- 1966-03-30 US US538871A patent/US3407168A/en not_active Expired - Lifetime
- 1966-03-30 DE DE1694577A patent/DE1694577B2/de active Pending
- 1966-03-30 ES ES0324899A patent/ES324899A1/es not_active Expired
- 1966-03-30 BE BE678686D patent/BE678686A/xx unknown
- 1966-03-31 CH CH466866A patent/CH467294A/de unknown
- 1966-03-31 NL NL666604288A patent/NL150484B/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2885378A (en) * | 1956-05-14 | 1959-05-05 | Monsanto Chemicals | Composition containing halogenated vinylidene resin plus non-volatile liquid monophenyl alkane plasticizer |
| US3296184A (en) * | 1963-02-14 | 1967-01-03 | Montedison Spa | Vulcanizable compositions of olefin polymers or copolymers and vulcanized articles obtained therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| NL150484B (nl) | 1976-08-16 |
| DE1694577B2 (de) | 1974-04-18 |
| GB1131915A (en) | 1968-10-30 |
| NL6604288A (forum.php) | 1966-10-03 |
| CH467294A (de) | 1969-01-15 |
| DE1694577A1 (de) | 1971-06-16 |
| BE678686A (forum.php) | 1966-09-30 |
| ES324899A1 (es) | 1967-02-16 |
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